JPS61231548A - Treatment of spent photographic solution and photographic automatic developing machine - Google Patents

Abstract

PURPOSE:To enable the dumping and incineration of a spent photographic soln. by allowing the soln. to be absorbed in a resin and putting it in a flexible vessel or a paper bag. CONSTITUTION:At least part of a spent photographic soln. is allowed to be absorbed in a resin. Any resin which absorbs the spent photographic soln. may be used as the resin, but a resin having high liq. absorbency is preferably used. The resin having high liq. absorbency absorbs >=30, preferably >=500 times as much liq. as the resin by weight, and the higher liq. absorbency is preferable from the viewpoint of treatment efficiency. It is preferable that the resin is combustible because after-treatment is advantageously carried out. A saponified starch-acrylonitrile graft copolymer is preferably used as the resin having high liq. absorbency.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Applications WI] The present invention relates to a method for treating waste photographic processing solution and an automatic photographic developing machine, and more particularly to a monogastric silver genide copying method and an automatic photographic developing machine.

[Prior Art] In general, photographic processing of silver halide photographic materials includes development, fixing, washing, etc. in the case of black and white materials, and color development, bleaching, and fixing in the case of color materials.

Processes such as water washing and stabilization are performed using a treatment liquid that has one or more of these functions.

In photographic processing, in which a large amount of light-sensitive material is processed, the components consumed during processing are replenished, and on the other hand, components that increase in the processing solution (such as bromide ions in the developer and silver complex salts in the fixer) are A method is adopted to maintain the performance of the processing solution at a constant level by removing the components of the processing solution and keeping the processing solution components constant. Some of the processing liquid is discarded to remove components.

In recent years, the system has been changing to a system in which the amount of replenishment, including the washing water used as a replenisher for washing, has been drastically reduced due to pollution and economic reasons. It is led out through a drainage pipe, diluted with waste water from washing water, and disposed of in a sewer, etc.

On the other hand, due to constraints from water resources, rising water supply and drainage costs, ease of installing automatic processors, and the work environment around automatic processors, stabilization treatments have been used in place of water washing in recent years.
Photographic processing using an automatic developing machine (17IAC), which does not require piping for water supply and drainage outside the automatic developing machine, is becoming popular. In such processing, it is said to be desirable to omit cooling water for keeping the temperature of the processing solution constant.

In photo processing, the only waste liquid from the automatic developing machine is the processing liquid that uses the replenisher, and the amount of waste liquid is significantly smaller than when washing with water is used. Therefore,
The piping outside the machine for supplying and draining liquid can be omitted, which is considered to be a disadvantage of conventional automatic processors, as it is difficult to move after installation to install the piping, and the leg space is small, making it easier to install. The disadvantages such as the large cost of piping work and the energy cost required for supplying hot water are all eliminated, and the extremely large advantage of achieving compactness and simplification to the point where it can be used as an office machine is demonstrated. .

However, even in relatively small-scale processing, the amount of photographic processing solution waste in such photographic processing is 1011 colors per day for processing X-ray photosensitive materials, and 3011 colors per day for processing photosensitive materials for printing plate making. 507 per day for photosensitive material processing
The amount of waste liquid is quite large, and since there is no piping outside the machine in an automatic developing machine such as the one described above, processing of the waste liquid is quite complicated.

In other words, when the waste liquid tank in an automatic processor is filled with waste liquid, it is complicated to detect it with a sensor or visually observe and replace the waste liquid tank. This has the disadvantage that the advantage of the automatic developing machine, which is that it can be installed on a clean 70-year-old or carpeted floor by eliminating the piping surrounding the developing machine, is lost.

Furthermore, the cost of the sensor is high, and collecting the waste liquid in a waste liquid collection container poses an aesthetic problem in that the container becomes dirty with the waste liquid, compared to the case where the waste liquid is guided through a drainage pipe and disposed of into the sewer.

Since many photographic processing solutions inherently contain components that are easily oxidized, they tend to generate tar or precipitate when exposed to air during storage. When two or more photographic processing solutions are mixed together and collected in a waste solution tank (this is usually the case), oxidation and precipitation are more likely to occur.
Tar and precipitates adhere to the bottom and walls of the waste liquid tank, solidify and become contaminated, creating a problem that worsens the working environment. In particular, waste liquids containing hydroquinone and phenidone as developing agents, and phenylenediamine derivatives as color developing agents are likely to turn into tar, and the droplets may stain clothes or irritate the skin, and thiosulfuric acid When waste liquid containing ions is oxidized, sulfur is precipitated, causing a problem.

If these two types of waste liquids are mixed, the degree of tar formation and precipitation will further increase, and if ferric salts of ethylenediaminetetraacetic acid are stored in these waste liquids, handling problems will be even more serious. (May cause precipitation of iron hydroxide and iron sulfide.

Another problem in treating waste liquid is that it cannot be directly incinerated because it is water. In systems without waste water from flushing, the BOD and 00D loads of waste water are large;
There is a problem that it cannot be directly flushed into the sewer system, so incineration is desired as the most advantageous method.

[Objective of the Invention] Accordingly, an object of the present invention is to provide a new method for treating photographic waste liquid that cannot be disposed of into a sewer system, etc., and another object is to provide a new method for treating photographic waste liquid discharged from a waterless automatic processor. The object of the present invention is to provide a method for processing photographic waste liquid that can be easily and safely collected without using sophisticated and complicated means such as a device for detecting the degree of filling of the waste liquid, and without worrying about soiling the floor. The purpose is to provide a method for treating photographic waste liquid that can be disposed of or incinerated in a flexible container or paper bag, and another purpose is to provide a method for treating photographic waste liquid that can be stored without taring or forming precipitates due to oxidation. To provide a method for collecting photographic waste liquid from an automatic processor in which a working environment is maintained in a good condition. Still another object is to provide a method for treating photographic waste liquid in which the waste liquid for recovering silver is absorbed into a resin so that it can be easily handled. Yet another object is to provide a compact and clean automatic photographic processor.

[Structure of the Invention] An object of the present invention is to provide a method for treating photographic waste liquid produced by processing photographic materials with a processing liquid, which is characterized in that at least a part of the photographic waste liquid is absorbed into a resin. achieved by the method.

Another object of the present invention is to provide a process for absorbing at least a portion of the photographic waste liquid into a resin, and a step of recovering silver from the resin that has absorbed the photographic waste liquid, in a method for treating photographic waste liquid generated by processing photographic materials with a processing liquid. This is achieved by a method for processing photographic waste liquid having the following properties.

Furthermore, an object of the present invention is to provide an automatic photographic processing machine having means for conveying photographic material and means for automatically supplying processing liquid, comprising:
This is achieved by an automatic photographic developing machine characterized by having a space in which resin absorbs at least a portion of photographic waste liquid.

The present invention will be described in detail below. The resin used in the present invention may be any resin as long as it absorbs photographic waste liquid, and highly liquid-absorbent resins are preferably used. The highly liquid-absorbing resin has a liquid-absorbing power that is 30 times or more than its own weight, more preferably 50 times or more, even more preferably 100 times or more, particularly preferably 500 times or more, and has high liquid absorption. This is preferable from the viewpoint of processing efficiency. Here, "liquid absorption power" refers to the value obtained by immersing sample IF of highly liquid-absorbent resin in photographic waste liquid for 5 minutes at room temperature and dividing the weight of the swollen sample by the weight of the sample before immersion.

Examples of photographic waste solutions include developing solutions with a specific gravity of 1.01 or higher, color developing solutions, fixing solutions, bleach-fixing solutions, bleaching solutions, stabilizers, stop solutions, image stabilizers, rinsing solutions, water washing substitute stabilizers, etc. Refers to one type of liquid or a mixture of two or more liquids after material processing, excluding washing water with a specific gravity of less than 1.01.

Liquid absorbency is related to liquid absorption speed as well as liquid absorption power, and the faster the liquid absorption speed, the better. In addition to liquid absorption power, liquid absorption speed is also considered when selecting a highly liquid absorbent resin. This is desirable.

Furthermore, it is desirable that the highly liquid-absorbent resin be capable of retaining photographic waste liquid for a long period of time, and that it should not be capable of syneresis under slight pressure, and that it is flammable, which is advantageous for post-treatment. It is particularly preferable for certain reasons.

The pH of photographic waste liquid is pH 3 to 13 for color developing solution,
Bleach solution and/or fixer solutions have a pH of 3 to 9, and waterless washing alternative stable solutions have a pH of 11 to 10. Those with small fluctuations in absorbency due to pH fluctuations are considered highly absorbent. Preferred as a resin.

The super absorbent resin may be used to absorb waste liquid, evaporate volatile substances such as water, and then repeatedly absorb the waste liquid two or more times so that the resin concentrates the substances contained in the waste liquid. .

Further, a highly liquid-absorbent resin that can absorb a specific volume of waste liquid while absorbing the waste liquid in a volume substantially smaller than the specific volume is advantageous in terms of compactness and is preferably used.
.

As the resin of the present invention, for example, those listed below can be used.

As seed polysaccharides, guar gum, castor bean gum, quince seed gum, tara gum, etc.

Seaweed polysaccharides include carrageenan, alginic acid, fur-shichiran, agar, etc.

As resin polysaccharides, arabinogalactan gum, gum arabic, gum tragacanth, gum karaya, etc.

Fruit polysaccharides such as pectin.

Rhizome polysaccharides include starch, koneiyaku, tororoa 1i, etc.

Furthermore, xanthan gum, xanfro, gardan, succinoglucan, schizophyllan, pullulan, gelatin,
Casein, Rupmin, Sheratsk, etc.

Starch derivatives, guar gum, locust bean gum derivatives, and cellulose derivatives that have been oxidized, carboxymethylated, hydroxyethylated, hydroxypropylated, carboxymethyl human tetraxyptetrapylated, and aminated.

As a 7kdf acid derivative, ammonium alginate,
Alginate propylene glycol ester, etc. O Vinyl type, Poval, Polyviny A/Hio+)
ton, polyvinyl metal relay, etc.

Acrylic materials include polyacrylic soda, polyacrylamide, etc.

Others, such as polyethylene oxide.

Next, preferred examples of the super absorbent resin used in the present invention will be listed. Jro.

(AJ grafted starch type (A-'L) starch-acrylonitrile graft polymer saponified product (A-2) starch-acrylic acid graft polymer above (
A-1) is based on Japanese Patent Application Laid-Open No. 49-43395 and U.S. Patent In
, xst, s6s, and the above (A-2) can be produced by the method described in Japanese Patent Publication No. 53-46199.

CB) Acrylic acid type (B-1) Sodium polyacrylate type (B-2) Vinyl alcohol-acrylic polyurethane type (B-27 can be used repeatedly by natural drying and/or forced drying) can.

A polymer having a repeating unit having the structural formula (07 below CI) or CTI), more preferably CI)
and Mata are polymers containing 10 to 70% (n) by weight and copolymerized with other ethylenically unsaturated monomers.

(I) In the ID R Tatami-gami formula, R is a hydrogen atom, a methyl group, or a hydrogen atom, 2 is an oxy group or an atom), n is O or 1, and R1 is , an alkylene group having 1 to 6 fa carbon atoms (including [substituted alkylene groups), a cycloalkylene group or arylene group having 5 to 6 carbon atoms,
an arylene alkylene group or an arylene bisalkylene group, wherein the alkylene moiety has 1 to 6 carbon atoms and the arylene moiety (optionally substituted) has 6 to 10 carbon atoms. arylene substituted with a hydrophilic polar group such as , which is an alkyl group having a carbon atom, H, Hm and R4 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; can be,
or together with N form a heterocyclic group which may optionally contain sulfur or oxygen atoms, M+ is a hydrogen atom, a soluble cation or a quaternary group having an alkyl group with up to 6 carbon atoms; An ammonium group includes an ammonium cation, and xe is an acid anion.

The halogen substituent on R can be bromine or chlorine, the alkylene group having 1 to 6 carbon atoms in R1 can be substituted with a hydroxyl group, and the 7-arylene alkylene group in R1 can be a phenylenemethylene group. , a phenyleneethylene group, a 7-ethylenepropylene group, and a phenylenebutylene group, and the arylenebisalkylene group of R1 includes a 7-ethylene dimethylene group.

Soluble cations of M include sodium and potassium.

The heterocyclic group formed from lBm and R4 and the M atom to which they are bonded includes pyridinium, imidazolium,
These include oxacillium, thiazolium and morpholium.

Acid anions of X include chloride, bromide, acetate, 1)-
) luenesulfonate, methanesulfonate, ethanesulfonate9, methylsulfate, ethylsulfate and perchlorate.

Examples of monomers derived from the repeating units CI) and CTI) include: M-(2-acrytetrayloxyethyl)-"*H,N-
Trimethylammonium tetralide, N-(2-hydroxy-3-methacryloyloxypropyl)-N, M, P
i-) Limethyltenmoeum chloride, N-(3-acrylicylmidoprobylnopyridinium chloride, N-(2-hydroxy-3-methacryloyloxyethyl-N,N,l!-)limethylammonium chloride, N-(2-methacryloyloxyethyl]-N.

IN-trimethylammonium iosito, N-(2-methacryloyloxyethyl) -N+N,N-)limethylammonium p-)luenesulfonate, H-(2-methacryloyloxyethyl) ” NtN
N-) Limethylammonium methosulfate, N-(2-methacryloyloxyethyl no N.

IN-trimethylammonium acetate, N-(2-
methacryloyloxyethyl)””IN N-)limethylammonium bromide, 1! -(2-methacryloyloxyethyl) -'tN N-)limethylammonium chloride, N-(2-methacryloyloxyethyl]-M.

M N-)limethylammonium ethyl sulfonate, H-(2-methacryloyloxyethyl no N.

・H,M-trimethylammonium nitrate, N-(
2-methacryloyloxyethyl) -N.

Nl! -) Limethylammonium phos7ate, N
-(3-7crylamide-3,3-dimethylpropyl)
-N,N,N-trimethylammonium methosulfate, N-vinylbenzyl-N,N,IJ-)limethylammonium chloride, N-benzyl-NN-dimethyl-N-vinylbenzylammonium chloride, N,N,M- ) Lihexyl N-vinylbenzylammonium chloride, N-(2-minoethylmethacrylamide hydrochloride, 2-aminoethyl methacrylate chloride, M-(3-7minoprovir]methacrylamide hydrochloride, 4-(N, N-diethyl-termino)-1-methylbutyl acrylate hydrochloride, 2-(N,M-diethyl-termino)-ethyl acrylate hydrochloride, 2-(N,M-diethyl-termino)-1-methylbutyl acrylate hydrochloride, 3- (M,M-diethyl7mino]p4pyr acrylate hydrochloride, N-(1,l,!-)limethyladennoprovir λacrylicylmidohydrocrylate, 2-(M,M-dimethylmino]ethyl Acrylate human chloride, 2-(M,M-dimethyl-minoethyl)ethyl methacrylate hydrochloride, N-(2-dimethyl-minoethyl)acrylamide hydrochloride, )I-(2-dimethyl-minoethyl methacrylate) 7 Mydohydrotetrachloride, 3-(N,li-dimethylamitsunopropyl acrylic 7
之hydrochloride, Sodium 4-acryloxybutane-1-sulfonate, Sodium 3-7acryloxybutane-1-sulfonate, Sodium 3-acryloxypropane-1-sulfonate, Sodium 2-ester Rilutemido 2-methylp4panesulfonate, Sodium 3-acrylamidopropane-1-sulfonate, Sodium 2-methacrylyloxyethyl-1-sulfonate, Sodium methacryloyloxybutane-1-sulfonate, Sodium number-methacryloyloxybutane-1-sulfonate, Sodium 2-methacrylicyloxyethane-1-sulfonate, sodium 3-methacrylicyloxypropane-1-sulfonate, sodium 2-methacrylicyloxypropane-1-sulfonate, sodium 2-methacrylicyloxypropane-1-sulfonate, and sodium 3-7crylamide-3-methylbutane-1
- Sulfonates.

The monomer of the general formula (I) and/or the monomer of the general formula (IC
The ethylenically unsaturated monomer to be copolymerized with the monomer is preferably one or more monomers having crosslinkable groups, such as 2- and hydroxyethyl methacrylate, 2-hydroxyethyl 7 It consists of acrylate and an active methylene group-containing monomer. Polymerized copolymerizable ethylenically unsaturated monomers of this type are described, for example, in U.S. Pat.
I/g No. 3゜554.98γ, No. 3.658,878, I/g No. 3゜929.482 and No. 3,939,
It is described in No. 130.

Preferred polymers for use in the present invention are from 10 to
70% by weight derived from or having repeating units of one or more of the monomers listed below: 2-amino/ethyl methacrylate hydroquaride, N-(2-methacryloyloxyethyl-N.

M, H-trimethylammonium chloride, H-(2-
methacrylyloxyethyl) -"tM, M-trimethylammonium methosulfate, sodium 2-methacryloxyethyl-1-sulfonate, and 2-(N,N-dimethylaminone ethyl methacrylate hydrochloride.

An acid addition salt conforming to the above structural formula (I) can be converted to the free amine when it is neutralized with a base.

The polymer useful in the present invention can be prepared by polymerizing appropriate monomers in an aqueous solution according to conventional methods.

The monomer of the structural formula (I) includes L H, Youum and B.

Edited by Nyqulat's Funotional'Mono
m@rs , MaroonDekker , engineering no
, New York (19) 4) and US Pat. No. 2,780,604. The monomer of structural formula (II) is described in U.S. Pat. Nos. 3,024,221 and 3,506,707.
Optionally, this polymer can be prepared by (a) quaternizing the polymer having amine groups with an alkylating agent or otherwise;
(b) They can be prepared by reacting an amine with a polymer having a group reactive with the amine, such as an active halogen group.

Such techniques are known in the art and are described in U.S. Pat. No. 3.488,706 and U.S. Pat.
No. 9,690 and Canadian Patent No. 601,958.

In the present invention, the resins listed above can be preferably used. Commercially available products include, for example, Sumikagel N-100 (manufactured by Sumikagel Co., Ltd.), Sumikagel 8P-520 (manufactured by Sumikagel Chemical Co., Ltd.), and Sumikagel S-! io (manufactured by Sumika Kagaku Kogyo ■), Sumikagel IP-1020 (manufactured by Sumika Kagaku Kogyo ■), Sumikagel?
-03 (manufactured by Sumika Kagaku Kogyo ■), Sumikagel? -51 (manufactured by Sumika Kagaku Kogyo ■), Sumikagel IF-7! S (manufactured by Sumiya Kagaku Kogyo ■), Sunwet E M-300 (manufactured by Sanyo Kasei ■), Sunwet E M-1000 (manufactured by Sanyo Kasei ■), Acryo Keepe 08) 1-P (manufactured by Tetsu Seikagaku ■), Lanseal 1 (manufactured by Nippon Exlan ■) etc. The highly liquid-absorbent resin used in the present invention preferably has a shape that easily absorbs liquid, and powder or granular materials with a diameter of about 0.01 N3s+s are suitable for handling. It can be used advantageously. Such a highly liquid-absorbent resin can be placed in a container that receives photographic waste liquid, or the resin can be sandwiched between paper or cloth that absorbs or permeates liquid, or a box made of such paper or cloth is used. All you have to do is put it in a container such as a bag and place it in a container that receives photographic waste liquid to absorb the undiluted solution. Further, the container for receiving the photographic waste liquid may be made of coated paper coated with a plastic film such as polyethylene. The container can also be folded and stored before use. More specifically, the following aspects (a) to (a) can be mentioned.

(b) Either line the tray at the bottom of the automatic processor that receives photographic waste liquid with a highly liquid-absorbing resin, or place the highly liquid-absorbent resin in a liquid-permeable container (cloth bag, paper box, plastic container with pores, etc.). Put the food in a tray and use it.

(b) A synthetic resin container (bottle, bucket, bag, etc.) containing highly liquid-absorbent resin is installed outside the automatic processor, and photographic waste liquid discharged from the automatic developer is guided to the container via a pipe. Let it absorb.

(c) In (a) and (b) above, an easily attachable and detachable cartridge containing a highly absorbent resin is used. The cartridge has at least one connection to the main body of the automatic processor other than the joint where waste liquid is discharged.
It is preferable to have two attachment/detachment joints. Since the cartridge becomes quite heavy by absorbing waste liquid, it is preferable to have a shape that supports it from the bottom of the cartridge, and for attachment and detachment, it is preferable that the supporting area be 70% or less of the bottom surface.

2) Guide the photographic waste liquid into a container that does not contain super absorbent resin,
The container is placed in a tray lined with a highly absorbent resin or a highly absorbent material using the resin (for example, a laminated structure in which a highly absorbent resin is sandwiched between two tissues). In this embodiment, even if the waste liquid overflows from the container, the floor will not be soiled, and therefore an alarm sensor and an automatic shut-off valve to prevent overflow can be omitted.Furthermore, it is sufficient to install a simple alarm sensor that is cheaper than the conventional one. .

Next, an example of an apparatus for implementing the present invention will be explained with reference to the drawings.

FIG. 1 is a schematic sectional view of an automatic processor for silver halide color photographic materials (film and paper).

In the figure, reference numeral 101 denotes a mounting portion for mounting a magazine 103 containing a roll of connected and wound color negative film or color paper that has been photographed, and is provided on the side wall of the main body 104 of the automatic processor.

The color negative film or color paper 102 of the film magazine attached to the mounting part 101 is attached to the main body entrance part 1.
05 into the main body 104, a color developing tank 106, a fixing tank 107, a bleach-fixing tank 108, a first stabilizing tank 109, and a second stabilizing tank 109.
After passing through a stabilizing tank 110 and being automatically developed, it is dried in a drying section 111 (having an openable/closable lid), taken out from a main body outlet 112, and then subjected to cutting and other processes to become a product.

Although not shown, a replenisher tank and piping for replenishing the replenisher into each of the processing tanks 106 to 110, piping and a first
There are piping etc. for introducing the over 70-liquid from the stabilizing tank 109 into the bleach-fixing tank IO8. 113 is a control system material chamber for adjusting the temperature of the processing liquid. 1laA, 114B and 1140 are containers for receiving photographic waste liquid (waste liquid containers), respectively.
115% to each processing tank 106 to 115B and 1150
This is a drain pipe for guiding photographic waste liquid from 110.

Inside the waste liquid containers 116m, 11511 and 1150,
Highly liquid absorbent resin containers 116mm, 116B and 116a made of flexible plastic film having pores on the entire surface
Place the super absorbent resins 11hum, 117B, and 11fa inside.

FIG. 2 is a schematic cross-sectional view of a modified automatic developing machine shown in FIG. The over 7 liquid of the color developing tank 106 is drained from the drain pipe 114.
The overflow liquid from the bleach-fix tank 108 is led to a waste liquid container 115A through a drain pipe 114B.
The liquid from the stable tank is drained through the drain pipe 1140.
Both of them are led to the waste liquid container 115B.◎ The waste liquid of the photographic processing liquid in the present invention includes a single waste liquid of the photographic processing liquid obtained when a known silver halide photographic light-sensitive material is processed with a known photographic processing liquid, and and mixtures of two or more arbitrary types of waste liquids, and the photographic processing liquids include the following.

Color developing solution: Includes a color developing solution with a pH of 7 or higher containing a developing agent, an alkaline agent, a preservative, and other additives as shown below.◎ The color developing agent includes an aromatic primary amino color developing agent. The main drug is included, and the herbal medicine includes mininophenol derivatives and p-phenylenediamine derivatives.

These may be salts of organic or inorganic acids, such as hydrochlorides, sulfates, p-)luenesulfonates, sulfites, sulfur salts, benzenesulfonates, etc. The concentration may range from 0.1 to 30p.

Examples of the above-mentioned minophenol-based developers include 0-aminophenol, p-aminophenol, 6-7minor 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1 , 4-dimethyl-benzene and the like.

In addition, as a p-7z=enediamine derivative, M −
M'-Dialkyl-p-phenylenediamine compounds Examples: M, M'-dimethyl-p-73 nylenediamine hydrochloride, ■-Methyl-p-phenylenediamine hydrochloride, H,
M'-dimethyl-p-7 2-diamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylaminonotluene, N-ethyl-M-/-methanesulfonamidoethyl-3-methyl-4-7minoaniline sulfate, N-ethyl-N-β-hydroxyethyl Completed minoaniline, 4-
Amino-3-methyl-N,N'-diethylaniline, 4
-Ryominnow Pi-(2-methoxyethyl-N-ethyl-3-methylryoniline-p-)luenesulfonate and the like are included.

Examples of alkaline agents include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, borax, and the like.

Preservatives include hydroxylamine, sulfites, and the like. Other additives include benzyl alcohol, alkali metal halides such as potassium chloride and potassium chloride, development regulators such as citradinic acid, various antifoaming agents and surfactants, and methanol and dimethylform. Organic solvents such as esteramide or dimethylsulfonate, and further antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic tll,
2-alcohol, hydroxamic acid, pentose or hexose, birogata-1,3-dimethyl ether, etc.
Furthermore, various chelating agents can be used as metal ion sequestering agents, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,11-diphosphonic acid, and aminotri(methylenephosphonic acid). ) or aminopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid. Acids and the like, polyhydroxy compounds and the like are included.

Actichemistry solution: An aqueous solution of the alkaline agent mentioned in the color developing solution.

Bleaching solution: As a bleaching agent, a metal complex salt of an organic acid such as a polycarboxylic acid, an aminocarboxylic acid (which may be an alkali metal salt, an ammonium salt, or a water-soluble amine salt) or an organic acid such as oxalic acid, citric acid, etc. Bleaching solutions having a pH of 2.0 or higher and containing coordinated metal ions such as , cobalt, and copper are included.

Specific examples of aminopolycarboxylic acids are listed below.

[11 Ethylenediaminetetraacetic acid [21 Diethylenetriaminepentaacetic acid [3] Ethylenediamine-M-(β-oxyethyl-N, N'
, M'-) diacetic acid [4] pyrenediaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihyrobovine diethylglycine citric acid (or tartaric acid) [9] ethyl Ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid Lllll Ethylene diamine tetraprobion [12] 7. Nylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [1aldiethylenetriaminepentaacetic acid pentasodium salt] [17] Ethylenediamine- N-(β-oxyethyl)
-M, M', N'-)riacetic acid sodium salt [18
] Propylene diamine tetraacetic acid sodium salt [19]
2) Liloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are used in a concentration of 5 to 450 ji/11, more preferably 20 to zsofi/l.

As a bleaching agent, a bleaching solution containing a persulfate (eg, potassium persulfate, sodium persulfate, etc.) in a concentration range of 5 to 30,071 is also included.

The bleaching solution includes a solution containing sulfite as a preservative, if necessary, in addition to the above-mentioned bleaching agent. Alternatively, it may be a bleaching solution containing iron ethylenediaminetetraacetate (IID complex salt bleaching agent) and a large amount of a halide such as ammonium bromide. As the halide, in addition to ammonium bromide, chloride hydrogen acid,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be contained.

The bleaching solution is disclosed in Japanese Patent Application Publication No. 46-280 and Japanese Patent Publication No. 45-8506.
No. 46-556, Belgian Patent No. 770.910
No., Special Publication No. 836 to 1973, No. 53-91354,
Various bleaching accelerators described in JP-A-54-71634 and JP-A-49-42349 may also be added.

Fixing solution: A compound that reacts with silver halide to form a water-soluble complex salt used as a fixing agent in ordinary fixing processes, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and potassium thiocyanate. , thiocyanate salts such as sodium thiocyanate and ammonium thiocyanate, thiourea, thioether, etc., in an amount of 5 g/1 or more within a soluble range. Furthermore, various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be used alone or in combination of two or more. What does it contain?
Those containing various fluorescent brighteners, antifoaming agents, or surfactants, preservatives such as hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds, and organic chelating agents such as aminopolycarboxylic acids. Alternatively, a fixing solution having a pH of 3.0 or more containing a stabilizer such as nitroalcohol mononitrate, an organic solvent such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. is included.

Bleach-fixing g: using a metal complex salt of an organic acid in the bleaching solution as a bleaching agent at a concentration ranging from about 0.1 to about 309/it;
The fixing agent includes a bleach-fixing solution containing the fixing agent in the fixing solution at a concentration up to a saturation amount, and those containing sulfite as a preservative;
Examples include those containing a buffer, and bleach-fixing solutions containing a bleaching agent and having a pH of 4, 0 or higher. Also, a bleach-fix solution consisting of iron ethylenediaminetetraacetate (IID complex salt bleach) and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer;
Or, conversely, a bleach-fix solution containing a large amount of a halide such as ammonium bromide, or a composition containing a combination of iron ethylenediaminetetraacetate (IIIj fl#l salt making agent) and a large amount of a halide such as ammonium bromide. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, and iodine. Potassium chloride, ammonium iodide, etc. are also included.

Stabilizing liquid: ammonium compounds such as ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate,
Ammonium phosphite, ammonium fluoride, acidic ammonium heptatide, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium heptathide, ammonium hydrogen sulfate, ammonium sulfate,
Ammonium chloride, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adibinanoate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, sulfate 72% sodium hydrogen oxide, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, M sulfur [27% sodium, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate , ammonium chelate, ammonium heptalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate,
Ammonium succinate, ammonium sulfanilate,
Amsonium tartrate, ammonium thioglycolate,
2,4.6-Dolinitrophenolammonium nat
t O,001 to 1,0 mol, chelating agents such as organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, specifically ethylenediamine diorthohydroxyphenylacetic acid, diaminopropane tetraacetic acid , nitritetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediamineniprobionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid,
Hydoxychetyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanedi11-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2°4-tricarboxylic acid, 1-hydroxy-1-pho! , honopropane-1,2,3-)licarboxylic acid, catechol-
Stable 3,5-disulfonic acid, sodium birophosphate, sodium tetrapolyline, sodium hexametaphosphate, etc. g, 1! 0.01 to 50 g per serving, and organic acid salts (citric acid, acetic acid, succinic acid, Scheric acid, benzoic acid, etc.)
, pHig ml agents (phosphate, borate, base number, sulfuric acid, etc.), antifungal agents (phenol derivatives, catechol derivatives, imidazo-/%/1llS conductors, triazole derivatives, thiabendazole derivatives, organic halogen compounds,
Other antifungal agents known as slime control agents in the paper-pulp industry) or fluorescent brighteners, surfactants, preservatives, Bi, Mg, Zn, Ni, A
J, an.

Stabilizers containing effective amounts of metal salts such as Ti, Zr, etc. are included.

Black and white developer: a developing agent such as 1-phenyl-3-pyrazolidone, metol and nohydroquinone, a preservative such as sulfite, an accelerator consisting of an alkali such as potassium carbonate, Inorganic or organic inhibitors such as potassium bromide, 2-methyl, benzimidazole, and methylbenzthiazole, water softeners such as polyphosphates, and surface overdevelopment prevention consisting of iodides and mercapto compounds. Included are black and white developers commonly used for silver halide photosensitive materials containing agents and the like.

If photographic waste liquid or developing agent (%) contains phenylenediamine derivative λ and/or thiosulfate ion, it will turn into tar or form a precipitate as described above. Applying the present invention to photographic waste liquid and absorbing it into a super absorbent resin prevents this phenomenon and is particularly effective. Also, since the waste liquid will not be splashed, it will not damage clothes or skin. Easy problems will also be improved.

When absorbing photographic waste liquid as described above into a highly absorbent material, it is also possible to absorb each type of processing liquid separately.
Two or more types can also be absorbed together. Preferred embodiments are described below.

(B) Color photographic processing (Part 1) Steps: color development → bleach-fixing → l1fl The waste liquid from stable color development is absorbed separately, and the waste liquid from bleach-fixing and stabilization are absorbed in separate super absorbent resins.

(cl) Color photographic processing (Part 2) Process: color development → bleaching → fixing → first stable → second stable The waste liquids from color development and bleaching and second stabilization are combined and absorbed into a super absorbent resin, followed by fixing and fixing. @1 The stable waste liquids are combined and absorbed into another super absorbent resin.

(c) Color photographic processing (Part 3) Process: color development → pre-fixing → bleach-fixing → first stable → second stable The waste liquid of color development and the waste liquid of second stable are each independently absorbed into super absorbent resin. let (Pre-fixing) Black and white photographic processing process: Development → Fixing → Water washing The waste liquid from development and the waste liquid from fixing are each absorbed separately into a superabsorbent resin, and the waste liquid from washing is discharged to the sewer.

Photographic processing steps other than those described above may be carried out in accordance with the above.

The highly liquid-absorbent resin that has absorbed the photographic waste liquid or the highly liquid-absorbent material containing the resin is disposed of or incinerated as is, but it may also be disposed of or incinerated after post-treatment such as evaporation or dehydration. When containing silver ions, it is preferable that the silver be recovered.

As a method for recovering silver, for example, it may be incinerated and recovered from the ashes in the incineration residue (silver in the ashes may be recovered by dissolving it with nitric acid and then electrolyzing it.

It is especially advantageous to solve the above-mentioned technical problems that arise when the camera is not equipped with a drainage pipe, or it is not limited to automatic processing machines such as this, but it is also useful for discharging some of the photographic waste liquid to sewers, etc. It is effective for photographic processing using automatic processors or for photographic processing without automatic processors, which cannot be disposed of separately.It is also effective for photographic materials that are processed with processing liquids, and the waste liquid of the processing liquid is high @liquid. The material is not limited to silver halide photographic materials as long as it is absorbed by a transparent resin.

〔Example〕

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 Color paper was produced by a conventional method. The silver halide used was silver chlorobromide (silver chloride 25 mol %), and it was coated on polythousand-coated paper so that the coated silver amount was 109/Zoo-, and after drying, it was used as a sample.

This sample was exposed to light using a color printer, and processed in accordance with the following steps using an automatic processor according to the conceptual diagram of an automatic processor shown in FIG.

Processing step (1) Color development 38°C 3 minutes 30 seconds (2)
Bleach fixing 38℃ 1 minute 30 seconds (3) Stabilization release 33℃ 3 minutes (4) Drying
75-80°C for about 2 minutes Processing solution composition [Color developing tank liquid] Benzyl alcohol 15aj Ethylene glycol 1f5jlj Potassium sulfite 2.0.9 Potassium bromide 1.3 p Sodium chloride o, zg Potassium carbonate
30.0Ii Hydroxylamine sulfate 3.0.91-Hydroxyethylidene-1,11-diphosphonic acid
0.69 Magnesium Chloride
0.9II 3-Methyl-4-amino-N-ethyl-N-(/-methanesulfonamidoethyl-aerin sulfate 5.5g Fluorescent brightener (Keikol PIC-0 manufactured by Shin Nisso Kako Co., Ltd.)
1. oIi Water was added to make IJ, and potassium hydroxide was added to adjust the pH to 10.20.

Color development replenisher] Benzyl alcohol 20aJ ethylene glycol 20-potassium sulfite 3. Ol vertical potassium
30.0Iihi, Doromydylamine ill [[+,og3-methyl-4-reminnow N-
Ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 7.51
11-Hytroxyethylidene-1,11-diphosphonic acid 0.6g Magnesium chloride 0.9Ji! 1. Firefly whitening agent (Keikol PK-0 manufactured by Shin Nisso Kako Co., Ltd.)
Add 1.077 water to make 1j, add potassium hydroxide or 5° sulfuric acid to pHI O,
F.

[Bleach-fix solution and replenisher] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 6Q,9 ethylenediaminetetraacetic acid 3Ii 7-ammonium thiosulfate (
70% solution) 1ooaj ammonium sulfite (40%
Solution) Add 27.5m water and l! and adjusted to pH 7.1 O by adding potassium carbonate [Stabilizing solution and replenishing solution] Sodium benzoate 0.511-Hydroxyethylidene-1,1-diphosphonic acid
1.077 Magnesium chloride 0.7I Polyvinylpyrrolidone O,lIi Ammonium hydroxide (
28 Rumor water ffI solution) 39 Adjusted the pH to 7.1 with acetic acid and potassium hydroxide.

Processing was carried out continuously up to 1000 sheets per cabinet (198Ii) per 1j. In an anhydrous washing system, the waste liquid container is preferably in the range of 1:6 to 2:3 (color developing waste liquid container capacity: bleach-fixing liquid waste liquid container capacity: 1:6 to 2:3); I used the one from During this process, when the processing solution was drained and overflowed to measure the total discharge amount, 2.2 mm of color developing waste solution and 6.21 mm of waste solution from bleach-fixing and stabilizing solution were discharged. Waste liquid from bleach-fixing and stabilizing solutions spilled from the waste liquid containers and contaminated the environment. In addition, it was difficult to take out the color developer waste solution from the automatic processor without spilling it, and the work took a long time.

On the other hand, when 1,000 cabinets were treated in the same way with 71 and 25 g of Sumikagel 5-50 in each container, it was found that there was no environmental pollution, the operation was simple, and the operator did not have to do anything. I was able to replace the waste liquid container in a single hour without soiling my clothes or clothes.

Surprisingly, even though 200 cabinets were processed, no waste liquid overflowed and no environmental pollution occurred.

This treated resin was left for one week, but no tarring or precipitate was formed.

Example 2 When the waste liquid absorption resin obtained by treating 1000 cabinets in Example 1 was incinerated at 700 to 1000°C, it was easily combusted.

In addition, the silver in the processing solution could be recovered from the ash in the burnt residue. As another method, silver in the ash was dissolved with nitric acid and then recovered by electrolysis.

[Effects of the Invention] According to the present invention, photographic waste liquid is absorbed by the highly absorbent W fat and becomes solid, so it is easy to handle and can be disposed of and incinerated in a flexible container or paper bag. Photographic waste liquid can be collected safely without scattering, which is the case with conventional methods of treating waste liquid as a liquid.Also, it is easy to expand the size of the waste liquid container horizontally and in the stacking direction, increasing storage capacity. This greatly reduces the need for alarm equipment and concerns about soiling the floor.

[Brief explanation of the drawing]

1 and 2 are schematic cross-sectional views showing an example of the device of the present invention. 101...Magazine attachment part 110...Second stabilization tank 102...Color negative film or color paper 1
11...Drying section 103...Magazine 112...Main body outlet 104...Automatic developing machine body 113...Control system equipment room 105...Main body inlet 114A, 114B and 114(]-Drainage liquid Pipe 106・
... Color developing tanks 115A, 1], 5B and 1150... Waste liquid container 1
07...Fixing tanks 116A, 116B and 1160...Super absorbent resin container 108...Bleach-fixing tanks 117A, 117B and 1170...Super absorbent resin 109...First stabilizing tank 2nd figure

Claims (1)

[Scope of Claims] 1) A method for treating photographic waste liquid produced by treating photographic materials with a processing liquid, which comprises at least one of the photographic waste liquids.
A method for processing photographic waste liquid, which is characterized by absorbing the liquid into a resin. 2) The method for treating photographic waste liquid according to claim 1, wherein the resin is a highly liquid-absorbing resin having a liquid-absorbing power of 50 times or more by weight. 3) The method for treating photographic waste liquid according to claim 1 or 2, wherein the photographic waste liquid contains a paraphenylenediamine derivative and/or a thiosulfate ion. 4) The method for treating photographic waste liquid according to claim 1, 2 or 3, wherein the resin is flammable. 5) A method for treating photographic waste liquid generated by processing photographic materials with a processing liquid, comprising the steps of absorbing at least a portion of the photographic waste liquid into a resin, and recovering silver from the resin formed by absorbing the photographic waste liquid. A method for processing photographic waste liquid characterized by: 6) The method for treating photographic waste liquid according to claim 5, wherein the resin is flammable. 7) The method for treating photographic waste liquid according to claim 5 or 6, wherein the resin is a highly liquid-absorbing resin having a liquid-absorbing power of 50 times or more by weight. 8) An automatic photographic developing machine having a means for transporting photographic materials and an automatic means for supplying a processing liquid, the automatic photographic developing machine having a space for absorbing at least a part of the photographic waste liquid into a resin. 9) The automatic photographic developing machine according to claim 8, wherein the automatic photographic developing machine does not have a washing tank. 10) The automatic photographic developing machine according to claim 8 or 9, wherein the photographic developing machine is not equipped with a water supply pipe, a cooling water supply pipe, or a drain pipe. 11) Claim 8, characterized in that the resin is a highly liquid-absorbing resin whose liquid-absorbing power is 50 times or more by weight,
The automatic photographic developing machine according to item 9 or 10.